CN102658162B - Catalyst for synthesizing ethylene amine and method for preparing ethylene amine - Google Patents
Catalyst for synthesizing ethylene amine and method for preparing ethylene amine Download PDFInfo
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- CN102658162B CN102658162B CN201210108743.1A CN201210108743A CN102658162B CN 102658162 B CN102658162 B CN 102658162B CN 201210108743 A CN201210108743 A CN 201210108743A CN 102658162 B CN102658162 B CN 102658162B
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- catalyst
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- ammonification
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- ammonia
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- 239000003054 catalyst Substances 0.000 title claims abstract description 89
- 238000000034 method Methods 0.000 title claims abstract description 44
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical compound NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 title abstract 5
- 230000002194 synthesizing effect Effects 0.000 title abstract 2
- 238000004176 ammonification Methods 0.000 claims abstract description 56
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000001257 hydrogen Substances 0.000 claims abstract description 24
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 24
- 229910052796 boron Inorganic materials 0.000 claims abstract description 16
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 6
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 6
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 6
- 229910052802 copper Inorganic materials 0.000 claims abstract description 5
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 5
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 5
- 229910052742 iron Inorganic materials 0.000 claims abstract description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 46
- 229910021529 ammonia Inorganic materials 0.000 claims description 23
- 239000012298 atmosphere Substances 0.000 claims description 20
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 8
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- 230000004913 activation Effects 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- 239000000969 carrier Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 43
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 19
- 230000000694 effects Effects 0.000 abstract description 13
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 33
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 26
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 25
- 206010013786 Dry skin Diseases 0.000 description 23
- 238000001035 drying Methods 0.000 description 23
- 239000000047 product Substances 0.000 description 22
- 239000003708 ampul Substances 0.000 description 17
- 239000008367 deionised water Substances 0.000 description 17
- 229910021641 deionized water Inorganic materials 0.000 description 17
- 239000010453 quartz Substances 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 238000005303 weighing Methods 0.000 description 17
- 230000008569 process Effects 0.000 description 16
- 239000007789 gas Substances 0.000 description 15
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 10
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 150000002466 imines Chemical class 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- HXMVNCMPQGPRLN-UHFFFAOYSA-N 2-hydroxyputrescine Chemical compound NCCC(O)CN HXMVNCMPQGPRLN-UHFFFAOYSA-N 0.000 description 4
- WFCSWCVEJLETKA-UHFFFAOYSA-N 2-piperazin-1-ylethanol Chemical compound OCCN1CCNCC1 WFCSWCVEJLETKA-UHFFFAOYSA-N 0.000 description 4
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000005576 amination reaction Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000013067 intermediate product Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical group CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- 125000003368 amide group Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000002738 chelating agent Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 125000003916 ethylene diamine group Chemical group 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- -1 polyethylene Polymers 0.000 description 2
- 238000004445 quantitative analysis Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 229910017813 Cu—Cr Inorganic materials 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002528 anti-freeze Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010835 comparative analysis Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229940031098 ethanolamine Drugs 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000003516 soil conditioner Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 1
- 229960001124 trientine Drugs 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8896—Rhenium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8953—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/14—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups
- C07C209/16—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups with formation of amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
- C07D295/023—Preparation; Separation; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
- C07D295/027—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
- C07D295/08—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms
- C07D295/084—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
- C07D295/088—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
- C07D295/12—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms
- C07D295/125—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms with the ring nitrogen atoms and the substituent nitrogen atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
- C07D295/13—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms with the ring nitrogen atoms and the substituent nitrogen atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a catalyst for synthesizing ethylene amine and a method for preparing ethylene amine. The catalyst comprises 1-40 wt% of a main active component, 0.1-20 wt% of an auxiliary agent, and a carrier processed by ammonification, wherein the main active component is Ni or Co, the auxiliary agent comprises one ore more of Fe, Cu, Ru, Re, K, Zn, B and other metal or oxides, and the ammonified carrier is ammonified SiO2 or Al2O3. The catalyst is characterized in that the used carrier needs to be ammonified. The ethylene amine product synthesized in hydrogen environment by using the catalyst of the invention to carry out ethanolamine ammonification reaction has high activity, high selectivity and stability.
Description
Technical field
The present invention relates to a kind of catalyst for the synthesis of ethyleneamines and application thereof.In more detail, relate to and a kind ofly be converted into the catalyst of the ethyleneamineses such as ethylenediamine (EDA), diethylenetriamine (DETA), AEEA (AEEA), piperazine (PIP), hydroxyethyl piperazine (HEP), aminoethyl piperazine (AEP) and prepare the method for ethyleneamines for monoethanolamine under the hydro condition (MEA) and ammonia.
Background technology
Ethylenediamine product is important industrial chemicals and fine-chemical intermediate, it mainly comprises the products such as ethylenediamine, diethylenetriamine, triethylene tetramine, TEPA, polyethylene polyamine, piperazine, can be used as epoxy curing agent, emulsifying agent, antifreeze, organic solvent and chemical analysis reagent; For the production of number of chemical auxiliary agents such as agriculture chemicals fungicide, Insecticides (tech) ﹠ Herbicides (tech), fuel, medicine, surfactant, metal chelating agents; Also can be used for producing chelating agent, corrosion inhibitor, soil conditioner, lubricant, lube oil additive and rubber accelerator and the industries such as weaving, papermaking, coating and adhesive, purposes is very extensive.
The method of industrial synthetic ethyleneamines mainly is dichloroethanes technique and monoethanolamine technique at present.
Dichloroethanes technique is serious to the corrosivity of equipment, energy consumption large and can cause serious environmental pollution, thereby causes production cost high, thereby this process route is eliminated just gradually.
The investment of monoethanolamine process route is low, and environmental pollution is little.Monoethanolamine technique is divided into again reducing process and condensation process, and wherein reducing process need to react under the high-pressure hydro condition, and the product major part is ethylenediamine; And condensation process need not to face hydrogen, and product is take cyclammonium as main.
Abroad the synthesis technique of industrial ethyleneamines is developed early, wherein BASF at first succeeds in developing monoethanolamine technique, and has realized industrialization the sixties in last century, and more American-European company adopts thereafter.Monoethanolamine process using Ni, the metallic catalysts such as Co, Cu that BASF develops, reaction temperature is 150~230 ℃, pressure is 20.0~30.0MPa, and its product mainly is ethylenediamine, diethylenetriamine, AEEA, piperazine, aminoethyl piperazine, hydroxyethyl piperazine etc.And domestic because production technology and production capacity with have a long way to go present industrial ethylenediamine product overwhelming majority dependence import abroad.
The amination in the presence of catalyst of monoethanolamine and ammonia generates ethylenediamine, because the intermediate product imines has higher reactivity than ammonia, therefore react the polyalkylenepolyamines accessory substance that inevitably produces complexity, so that the yield of ethylenediamine reduces and cause product separation difficult.Method commonly used can improve the selective of product, but conversion ratio reduces, and has affected the production capacity of ethylenediamine.Therefore, need a kind of catalyst can not only improve the selective of target product, and keep good amination conversion ratio.
US5068330 adopts different nickel based metal catalyst, add the noble metals such as Ir, Pt, Ru, at 120~300 ℃, the monoethanolamine conversion ratio is 20%~45%, and the ethylenediamine that generates selectively is 15%~55%, and diethylenetriamine selectively is 10%~20%.The selective all difficulties of the monoethanolamine conversion ratio of this catalyst and ethylenediamine reach requirement, and repeatedly add continuously noble metal in preparation process, have increased complexity and the production cost of technological operation.
US4642303 has reported that under the effect of Ni-Cu-Cr catalyst monoethanolamine aminating reaction temperature is conducive to the generation of ethylenediamine at low temperatures.
US4209424 has reported the impact of nickel loading on catalyst activity, wherein finds the increase along with nickel loading, and the conversion ratio of feed ethanol amine improves constantly, and is higher selective but reaction has cyclammonium (such as piperazine).
US4123462 points out that catalyst activity and carrier material have close relationship, wherein changes the surface propertys such as surface area, hole dimension, pore volume and support shapes of carrier, will affect within the specific limits the activity of catalyst.
But, the catalyst of above-mentioned prior art and the method for preparing ethyleneamines active, selective and stable etc. one or more aspect needs further improve.
Summary of the invention
The purpose of this invention is to provide a kind of catalyst for the synthesis of ethyleneamines and prepare the method for ethyleneamines, described catalyst and the method for preparing ethyleneamines can realize with lower one or more: (1) makes monoethanolamine face the hydrogen amination and produces ethyleneamines and can realize under lower reaction pressure, (2) the flexible composition of modulation ethyleneamines of modulation reaction condition, (3) reduce process units one-time investment and production cost, (4) realization is easy to operate, (5) activity of raising catalyst, (6) improve selective to product, (7) conversion ratio of raising raw material, and the stability of (8) raising method.
The present inventor finds: carrier material and catalyst activity have close relationship, and the carrier that catalyst is adopted carries out the ammonification processing, because carrier S iO
2Or Al
2O
3The surface on exist a large amount of hydroxyls to make carrier surface be sour environment, be conducive to the polymerization of intermediate product imines, and carrier surface by ammonification after, the a large amount of hydroxyl in surface is converted into amido, thereby carrier is alkaline environment, the possibility that this has just reduced the imines polymerization has improved the activity, selective and stable of catalyst; Can realize thus one or more in the above-mentioned purpose.
Therefore, in one aspect, the invention provides a kind of catalyst for the synthesis of ethyleneamines, carrier three parts that described catalyst was processed by main active component, auxiliary agent and ammonification form, wherein said main active component is selected from one or more in the group that is comprised of Ni and Co, and described auxiliary agent is selected from one or more in the group that is comprised of Fe, Cu, Ru, Re, K, Zn and B and their oxides separately; The carrier that described ammonification was processed is by being selected from by SiO
2And Al
2O
3One or more carriers in the group that forms are processed through ammonifications and are obtained, and described ammonification is processed and comprised: carrier and ammonia source are contacted 0.5 to 24 hour 200 to 400 ℃ temperature.
In a preferred embodiment, the specific area of described carrier is 150~350m
2/ g, and average pore size is 8-80nm.
In another preferred embodiment, described ammonia source is selected from one or more in the group that is comprised of ammonia, liquefied ammonia, ammoniacal liquor and urea.
In another preferred embodiment, described main active component accounts for 1~40% in the gross weight of described catalyst, and preferred 5~30%.
In another preferred embodiment, described auxiliary agent accounts for 0.1~20% in the gross weight of described catalyst, and preferred 0.1~15%.
In yet another aspect, the invention provides a kind of method for prepared ethyleneamines by monoethanolamine and ammonia, described method comprises: under described catalyst exists, under hydro condition monoethanolamine and ammonia are converted into ethyleneamines in the above.
In a preferred embodiment, described method is 135~200 ℃ in temperature, and pressure is that the liquid air speed of 6.0~22.0MPa and monoethanolamine is 0.3~1.5h
-1Condition under carry out.
In another preferred embodiment, described catalyst was normal pressure in hydrogen atmosphere and at pressure before using, and temperature is that 150~400 ℃ and hydrogen gas space velocity are 500~4000h
-1Condition under reduction activation.
The specific embodiment
More specifically, the invention provides a kind of loaded catalyst for the synthesis of ethylenediamine product, the carrier of being processed by main active component, auxiliary agent and ammonification forms, main active component is Ni and/or Co, and auxiliary agent is one or more in the group that forms of Fe, Cu, Ru, Re, K, Zn and B and their oxide separately; Carrier is selected SiO
2And/or Al
2O
3, and carrier has passed through the ammonification specially treated.Wherein, catalyst prepares by infusion process, wherein uses the solution impregnating carrier of the soluble-salt of Ni and/or Co, and described soluble-salt is nitrate, chlorate, acetate, oxalates, sulfate, citrate or other soluble-salt of Ni and/or Co.Main active component accounts for 1~40% in total catalyst weight; Auxiliary agent accounts for 0.1~20% in total catalyst weight; Carrier S iO
2Or Al
2O
3Specific area be 150~350m
2/ g, average pore size is 8-80nm.Carrier S iO
2And/or Al
2O
3Adopting ammonia, liquefied ammonia, ammoniacal liquor or urea to carry out ammonification processes.
Catalyst of the present invention is reduction activation in hydrogen atmosphere before application: pressure is normal pressure, and temperature is 150~400 ℃, and hydrogen gas space velocity is 500~4000h
-1Monoethanolamine and ammonia are converted into the reaction condition of ethylenediamine product under hydro condition: temperature is 135~200 ℃, and pressure is 6.0~22.0MPa, and the liquid air speed of monoethanolamine is 0.3~1.5h
-1
Reactor of the present invention can adopt fixed bed reactors, paste state bed reactor or trickle bed reactor.Preferred trickle bed reactor wherein.
In the reaction system of the present invention, can be directly with the monoethanolamine of liquid state and ammonia mixture be pumped in the preheater be preheated to 135~200 ℃ after hydrogen mixes after enter into trickle bed reactor.
This catalyst is applied in the reaction of monoethanolamine and ammonia under the hydro condition, shown excellent activity, selective and stable, the ethylenediamine product of generation comprises the ethyleneamineses such as ethylenediamine, diethylenetriamine, AEEA, piperazine, aminoethyl piperazine, hydroxyethyl piperazine.
Among the present invention, hydro condition refers under the condition of hydrogen existence.
The present invention compared with prior art, its significant effect is: the carrier S iO of catalyst of the present invention
2Or Al
2O
3Adopting ammonia, liquefied ammonia, ammoniacal liquor or urea to carry out ammonification processes.Because carrier S iO
2Or Al
2O
3The surface on exist a large amount of hydroxyls to make carrier surface be sour environment, be conducive to the polymerization of intermediate product imines and produce a large amount of accessory substances, thereby reduced the selective of ethylenediamine.And carrier surface by ammonification after, the surface a large amount of hydroxyls be converted into amido and be alkalescence, this has just reduced the possibility of imines polymerization, has improved selective and stable.After the carrier loaded main active component and auxiliary agent after the processing, be applied in the reaction of monoethanolamine and ammonia under the hydro condition, shown excellent activity, selective and stable, optimized reaction condition, realize the flexible modulation of ethylenediamine product, provide possibility for industrial production adapts to market fluctuation.Temperature, the pressure of its operation process conditions are starkly lower than prior art.Manufacturing condition optimization can reduce the pressure requirement to consersion unit, reduces one-time investment and the production cost of reaction unit, reduces simultaneously operation easier.
Embodiment
Below in conjunction with embodiment method of the present invention being described further, is not limitation of the invention.Unless otherwise noted, the part among the application, percentage and content are by weight.
Embodiment 1:
5%Ni-15%Re-1.2%B/SiO
2The preparation of catalyst and application
Take by weighing 10 gram carrier S iO
2(20-40 order) is with carrier S iO
2Be loaded in the quartz ampoule, under the inert atmosphere, then 200 ℃ of dryings 5 hours introduce 10% ammonia-hydrogen mixed gas (molar content), and the ammonification temperature is 300 ℃, 5 hours ammonification time.With 2.477 gram Ni (NO
3)
26H
2O, 2.161 gram NH
4ReO
4With 0.686 gram H
3BO
3Be dissolved in the 12ml deionized water.Flood the SiO that above-mentioned ammonification was processed with half of this aqueous solution
2Carrier dries naturally, and 120 ℃ of dryings are 4 hours subsequently, and then 500 ℃ of roastings are 4 hours.Then, flood for the second time the SiO that above-mentioned ammonification was processed with above-mentioned remaining second half aqueous solution
2Carrier, then nature dries, 120 ℃ of dryings 4 hours, 500 ℃ of roastings 4 hours.Before catalyst uses, (normal pressure, 2000h in 375 ℃ of hydrogen streams
-1) reduced 4 hours.When reactor temperature cools to 160 ℃ naturally, boost to 8MPa, behind the system stability, with NH
3The liquid of/monoethanolamine=10 pump of flowing through is squeezed in the reactor, and the liquid air speed of regulating monoethanolamine is 0.5h
-1, H
2/ NH
3/ monoethanolamine=0.25: 10: 1 (mol ratio) reacts, 50 hours reaction time, sample analysis.SE-30 capillary chromatographic column, fid detector, DMF are that interior mark carries out quantitative analysis, and reaction result sees Table 1.
Embodiment 2:
15%Ni-3.6%Re-1.2%B/SiO
2The preparation of catalyst and application
Take by weighing 10 gram carrier S iO
2(20-40 order) is with carrier S iO
2Be loaded in the quartz ampoule, under the inert atmosphere, then 200 ℃ of dryings 5 hours introduce 20% ammonia-hydrogen mixed gas (molar content), and the ammonification temperature is 300 ℃, 5 hours ammonification time.With 7.432 gram Ni (NO
3)
26H
2O, 0.518 gram NH
4ReO
4With 0.686 gram H
3BO
3Be dissolved in the 12ml deionized water.All the other preparation processes and evaluating catalyst scheme are referring to embodiment 1.Reaction result sees Table 1.
Embodiment 3:
30%Ni-0.2%Re-15%K/SiO
2The preparation of catalyst and application
Take by weighing 10 gram carrier S iO
2(20-40 order) is with carrier S iO
2Be loaded in the quartz ampoule, under the inert atmosphere, then 200 ℃ of dryings 5 hours introduce 50% ammonia-hydrogen mixed gas (molar content), and the ammonification temperature is 300 ℃, 5 hours ammonification time.With 14.864 gram Ni (NO
3)
26H
2O, 0.029 gram NH
4ReO
4With 3.879 gram KNO
3Be dissolved in the 12ml deionized water.All the other preparation processes and evaluating catalyst scheme are referring to embodiment 1.Reaction result sees Table 1.
Embodiment 4:
15%Ni-3.6%Cu-1.2%B/SiO
2The preparation of catalyst and application
Take by weighing 10 gram carrier S iO
2(20-40 order) is with carrier S iO
2Be loaded in the quartz ampoule, under the inert atmosphere, then 200 ℃ of dryings 5 hours introduce 20% ammonia-hydrogen mixed gas (molar content), and the ammonification temperature is 300 ℃, 5 hours ammonification time.With 7.432 gram Ni (NO
3)
26H
2O, 1.369 gram Cu (NO
3)
23H
2O and 0.686 gram H
3BO
3Be dissolved in the 12ml deionized water.All the other preparation processes and evaluating catalyst scheme are referring to embodiment 1.Reaction result sees Table 1.
Embodiment 5:
15%Co-3.6%Re-1.2%B/SiO
2The preparation of catalyst and application
Take by weighing 10 gram carrier S iO
2(20-40 order) is with carrier S iO
2Be loaded in the quartz ampoule, under the inert atmosphere, then 200 ℃ of dryings 5 hours introduce 20% ammonia-hydrogen mixed gas (molar content), and the ammonification temperature is 300 ℃, 5 hours ammonification time.With 7.408 gram Co (NO
3)
2H
2O, 0.518 gram NH
4ReO
4With 0.686 gram H
3BO
3Be dissolved in the 12ml deionized water.All the other preparation processes and evaluating catalyst scheme are referring to embodiment 1.Reaction result sees Table 1.
Embodiment 6:
5%Ni-8%Re-1.2%B/Al
2O
3The preparation of catalyst and application
Take by weighing 10 gram carrier A l
2O
3(20-40 order) is with carrier A l
2O
3Be loaded in the quartz ampoule, under the inert atmosphere, then 200 ℃ of dryings 5 hours introduce 10% ammonia-hydrogen mixed gas (molar content), and the ammonification temperature is 300 ℃, 5 hours ammonification time.With 2.477 gram NiCl
26H
2O, 1.152 gram NH
4ReO
4With 0.686 gram H
3BO
3Be dissolved in the 12ml deionized water.All the other preparation processes and evaluating catalyst scheme are referring to embodiment 1.Reaction result sees Table 1.
Embodiment 7:
15%Ni-2%Re-1.2%B/Al
2O
3The preparation of catalyst and application
Take by weighing 10 gram carrier A l
2O
3(20-40 order) is with carrier A l
2O
3Be loaded in the quartz ampoule, under the inert atmosphere, then 200 ℃ of dryings 5 hours introduce 20% ammonia-hydrogen mixed gas (molar content), and the ammonification temperature is 300 ℃, 5 hours ammonification time.With 7.432 gram Ni (NO
3)
26H
2O, 0.288 gram NH
4ReO
4With 0.686 gram H
3BO
3Be dissolved in the 12ml deionized water.All the other preparation processes and evaluating catalyst scheme are referring to embodiment 1.Reaction result sees Table 1.
Embodiment 8:
30%Ni-2%Re-1.2%B/Al
2O
3The preparation of catalyst and application
Take by weighing 10 gram carrier A l
2O
3(20-40 order) is with carrier A l
2O
3Be loaded in the quartz ampoule, under the inert atmosphere, then 200 ℃ of dryings 5 hours introduce 50% ammonia-hydrogen mixed gas (molar content), and the ammonification temperature is 300 ℃, 5 hours ammonification time.With 12.712 gram Ni (CH
3COO)
26H
2O, 0.288 gram NH
4ReO
4With 0.686 gram H
3BO
3Be dissolved in the 12ml deionized water.All the other preparation processes and evaluating catalyst scheme are referring to embodiment 1.Reaction result sees Table 1.
Embodiment 9:
15%Ni-0.2%Re-10%Zn/Al
2O
3The preparation of catalyst and application
Take by weighing 10 gram carrier A l
2O
3(20-40 order) is with carrier A l
2O
3Be loaded in the quartz ampoule, under the inert atmosphere, then 200 ℃ of dryings 5 hours introduce 20% ammonia-hydrogen mixed gas (molar content), and the ammonification temperature is 200 ℃, 5 hours ammonification time.With 6.356 gram Ni (CH
3COO)
26H
2O, 0.029 gram NH
4ReO
4With 4.549 gram Zn (NO
3)
26H
2O is dissolved in the 12ml deionized water.All the other preparation processes and evaluating catalyst scheme are referring to embodiment 1.Reaction result sees Table 1.
Embodiment 10:
15%Ni-3.6%Re-0.2%Zn/Al
2O
3The preparation of catalyst and application
Take by weighing 10 gram carrier A l
2O
3(20-40 order) is with carrier A l
2O
3Be loaded in the quartz ampoule, under the inert atmosphere, then 200 ℃ of dryings 5 hours introduce 20% ammonia-hydrogen mixed gas (molar content), and the ammonification temperature is 300 ℃, 5 hours ammonification time.With 7.432 gram Ni (NO
3)
26H
2O, 0.518 gram NH
4ReO
4With 0.091 gram Zn (NO
3)
26H
2O is dissolved in the 12ml deionized water.All the other preparation processes and evaluating catalyst scheme are referring to embodiment 1.Reaction result sees Table 1.
Embodiment 11:
30%Ni-2%Re/Al
2O
3The preparation of catalyst and application
Take by weighing 10 gram carrier A l
2O
3(20-40 order) is with carrier A l
2O
3Be loaded in the quartz ampoule, under the inert atmosphere, then 200 ℃ of dryings 5 hours introduce 50% ammonia-hydrogen mixed gas (molar content), and the ammonification temperature is 300 ℃, 5 hours ammonification time.With 14.864 gram Ni (NO
3)
26H
2O and 0.288 gram NH
4ReO
4Be dissolved in the 12ml deionized water.All the other preparation processes and evaluating catalyst scheme are referring to embodiment 1.Reaction result sees Table 1.
Embodiment 12:
15%Ni-2%Re-12%B/Al
2O
3The preparation of catalyst and application
Take by weighing 10 gram carrier A l
2O
3(20-40 order) is with carrier A l
2O
3Be loaded in the quartz ampoule, under the inert atmosphere, then 200 ℃ of dryings 5 hours introduce 20% ammonia-hydrogen mixed gas (molar content), and the ammonification temperature is 300 ℃, 5 hours ammonification time.With 7.432 gram Ni (NO
3)
26H
2O, 0.288 gram NH
4ReO
4With 6.86 gram H
3BO
3Be dissolved in the 12ml deionized water.All the other preparation processes and evaluating catalyst scheme are referring to embodiment 1.Reaction result sees Table 1.
Embodiment 13:
5%Co-15%Cu-1.2%K/Al
2O
3The preparation of catalyst and application
Take by weighing 10 gram carrier A l
2O
3(20-40 order) is with carrier A l
2O
3Be loaded in the quartz ampoule, under the inert atmosphere, then 200 ℃ of dryings 5 hours introduce 10% ammonia-hydrogen mixed gas (molar content), and the ammonification temperature is 200 ℃, 5 hours ammonification time.With 2.469 gram Co (NO
3)
2H
2O, 5.703 gram Cu (NO
3)
23H
2O and 0.310 gram KNO
3Be dissolved in the 12ml deionized water.All the other preparation processes and evaluating catalyst scheme are referring to embodiment 1.Reaction result sees Table 1.
Embodiment 14:
15%Co-3.6%Re-1.2%B/Al
2O
3The preparation of catalyst and application
Take by weighing 10 gram carrier A l
2O
3(20-40 order) is with carrier A l
2O
3Be loaded in the quartz ampoule, under the inert atmosphere, then 200 ℃ of dryings 5 hours introduce 20% ammonia-hydrogen mixed gas (molar content), and the ammonification temperature is 300 ℃, 5 hours ammonification time.With 7.408 gram Co (NO
3)
2H
2O, 0.518 gram NH
4ReO
4With 0.686 gram H
3BO
3Be dissolved in the 12ml deionized water.All the other preparation processes and evaluating catalyst scheme are referring to embodiment 1.Reaction result sees Table 1.
Embodiment 15:
30%Co-2%Re-1.2%B/Al
2O
3The preparation of catalyst and application
Take by weighing 10 gram carrier A l
2O
3(20-40 order) is with carrier A l
2O
3Be loaded in the quartz ampoule, under the inert atmosphere, then 200 ℃ of dryings 5 hours introduce 50% ammonia-hydrogen mixed gas (molar content), and the ammonification temperature is 300 ℃, 5 hours ammonification time.With 14.816 gram Co (NO
3)
2H
2O, 0.288 gram NH
4ReO
4With 0.686 gram H
3BO
3Be dissolved in the 12ml deionized water.All the other preparation processes and evaluating catalyst scheme are referring to embodiment 1.Reaction result sees Table 1.
Embodiment 16:
The stability test of catalyst is pressed the catalyst of the method for preparing catalyst preparation among the embodiment 7 in fixed bed reactors, and reaction condition: temperature is 160 ℃, and pressure is 8MPa, and the liquid air speed of monoethanolamine is 0.5h
-1, H
2/ NH
3/ monoethanolamine=0.25: 10: 1 (mol ratio) reacts, every 24 hours sample analysis of reaction.SE-30 capillary chromatographic column, fid detector, DMF are that interior mark carries out quantitative analysis, and 1000 hours reaction result shows that the activity and selectivity of catalyst is basic identical.
Comparative Examples 1:
The 15%Ni-3.6%Re-1.2%B/SiO that carrier is processed without ammonification
2The preparation of catalyst and application
Take by weighing 10 gram carrier S iO
2(20-40 order) is with carrier S iO
2Be loaded in the quartz ampoule, under the inert atmosphere, 200 ℃ of dryings 5 hours.With 7.432 gram Ni (NO
3)
26H
2O, 0.518 gram NH
4ReO
4With 0.686 gram H
3BO
3Be dissolved in the 12ml deionized water.Flood above-mentioned SiO with half of this aqueous solution
2Carrier dries naturally, and 120 ℃ of dryings are 4 hours subsequently, and then 500 ℃ of roastings are 4 hours.Then, flood for the second time the above-mentioned SiO that is loaded with metal with above-mentioned remaining second half aqueous solution
2Carrier, then nature dries, 120 ℃ of dryings 4 hours, 500 ℃ of roastings 4 hours.The evaluating catalyst scheme is referring to embodiment 1.
Comparative Examples 2:
The 15%Co-3.6%Re-1.2%B/Al that carrier is processed without ammonification
2O
3The preparation of catalyst and application.
Take by weighing 10 gram carrier A l
2O
3(20-40 order) is with carrier A l
2O
3Be loaded in the quartz ampoule, under the inert atmosphere, 200 ℃ of dryings 5 hours.With 7.408 gram Co (NO
3)
2H
2O, 0.518 gram NH
4ReO
4With 0.686 gram H
3BO
3Be dissolved in the 12ml deionized water.Flood above-mentioned Al with half of this aqueous solution
2O
3Carrier dries naturally, and 120 ℃ of dryings are 4 hours subsequently, and then 500 ℃ of roastings are 4 hours.Then, flood for the second time the above-mentioned Al that is loaded with metal with above-mentioned remaining second half aqueous solution
2O
3Carrier, then nature dries, 120 ℃ of dryings 4 hours, 500 ℃ of roastings 4 hours.The evaluating catalyst scheme is referring to embodiment 1, and reaction result sees Table 1.
The selective following calculating of the molar yield of monoethanolamine and molar product:
The conversion ratio of monoethanolamine: Conv. (%)=(1-N
EDA* C
EDA/ (N
EDA* C
EDA+ ∑ Ni * Ci)) * and 100% product selective: Si=(Ni * Ci/ ∑ Ni * Ci) * 100%
Wherein:
N
EDA: the molal quantity of monoethanolamine in the product;
C
EDA: the carbon number of monoethanolamine;
Ni: the molal quantity of product i in the product;
Ci: the carbon number of product i in the product.
Embodiment 2 is identical with the catalytic component of reference examples 1, and different is the carrier process ammonification processing of embodiment 2, and the carrier of reference examples 1 is processed through ammonification, comparative result, be not difficult to find that the conversion ratio of monoethanolamine has improved 31%, the selective of ethylenediamine improved 32%.
Embodiment 14 is identical with the catalytic component of reference examples 2, and different is the carrier process ammonification processing of embodiment 14, and the carrier of reference examples 2 is processed through ammonification, comparative result, be not difficult to find that the conversion ratio of monoethanolamine has improved 34%, the selective of ethylenediamine improved 27%.
Comparative analysis result above comprehensive can assert, after catalyst carrier adopts ammonification to process, can be at described catalyst and prepare and realize in the method for ethyleneamines with lower one or more: realize under lower reaction pressure (1), (2) the flexible composition of modulation ethyleneamines of modulation reaction condition, (3) reduce process units one-time investment and production cost, (4) realization is easy to operate, (5) activity of raising catalyst, (6) improve selective to product, the conversion ratio of (7) supplying raw materials, and (8) raising method is stable.
Claims (8)
1. catalyst for the synthesis of ethyleneamines, carrier three parts that described catalyst was processed by main active component, auxiliary agent and ammonification form, wherein said main active component is selected from one or more in the group that is comprised of Ni and Co, and described main active component accounts for 1~40% in the gross weight of described catalyst; Described auxiliary agent is selected from one or more in the group that is comprised of Fe, Cu, Ru, Re, K, Zn and B and their oxides separately, and described auxiliary agent accounts for 0.1~20% in the gross weight of described catalyst; The carrier that described ammonification was processed is by being selected from by SiO
2And Al
2O
3One or more carriers in the group that forms are processed through ammonifications and are obtained, and described ammonification is processed and comprised: carrier and ammonia source are contacted 0.5 to 15 hour 150 to 400 ℃ temperature.
2. according to catalyst claimed in claim 1, the specific area of wherein said carrier is 150~350m
2/ g, and average pore size is 8-80nm.
3. according to catalyst claimed in claim 1, wherein said ammonia source is selected from one or more in the group that is comprised of ammonia, liquefied ammonia, ammoniacal liquor and urea.
4. according to catalyst claimed in claim 1, wherein said main active component accounts for 5~30% in the gross weight of described catalyst.
5. according to catalyst claimed in claim 1, wherein said auxiliary agent accounts for 0.1~15% in the gross weight of described catalyst.
6. method that is used for being prepared by monoethanolamine and ammonia ethyleneamines, described method comprises: in the presence of catalyst claimed in claim 1, under hydro condition monoethanolamine and ammonia are converted into ethyleneamines.
7. according to method claimed in claim 6, wherein said method is 135~200 ℃ in temperature, and pressure is that the liquid air speed of 6.0~22.0MPa and monoethanolamine is 0.3~1.5h
-1Condition under carry out.
8. in accordance with the method for claim 6, wherein said catalyst was normal pressure in hydrogen atmosphere and at pressure before using, and temperature is that 150~400 ℃ and hydrogen gas space velocity are 500~4000h
-1Condition under reduction activation.
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CN106669836A (en) * | 2015-11-05 | 2017-05-17 | 南通市永顺化工有限公司 | Catalyst for preparing ethyleneamine |
CN106669824A (en) * | 2015-11-05 | 2017-05-17 | 南通市永顺化工有限公司 | Catalyst applied to preparation of ethylenediamine |
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CN101704753A (en) * | 2009-11-17 | 2010-05-12 | 中国科学院大连化学物理研究所 | Method for preparing ethylene diamine from ethanolamine and ammonia serving as raw materials under hydrogen condition |
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- 2012-04-13 CN CN201210108743.1A patent/CN102658162B/en active Active
- 2012-05-24 IN IN7644DEN2014 patent/IN2014DN07644A/en unknown
- 2012-05-24 WO PCT/CN2012/075989 patent/WO2013152548A1/en active Application Filing
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CN101406845A (en) * | 2008-12-08 | 2009-04-15 | 西安近代化学研究所 | Amination catalyst and preparation method thereof |
CN101829581A (en) * | 2010-05-11 | 2010-09-15 | 广西壮族自治区化工研究院 | Catalyst for amination of ethanolamine to sysnthsize ethylene diamine and preparation method thereof |
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IN2014DN07644A (en) | 2015-05-15 |
WO2013152548A1 (en) | 2013-10-17 |
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